CN101323624B - Nitrogen heterocyclic ring double carbine metal complex , preparation and use thereof - Google Patents
Nitrogen heterocyclic ring double carbine metal complex , preparation and use thereof Download PDFInfo
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Abstract
The invention discloses a circular nitrogen heterocyclic ring dual-carbene metal complex which is connected by tetramethylbenzenes and a preparation method thereof. The azacyclo-dual carbene of the invention can be expressed by formula (I), please refer to the formula on the right, wherein, R1 or R2 serves independently or in combination as hydrogen or C1-C6 organic group; C1-C6 organic group is one or more selected from alkyl, branched alkyl, naphthene base, alkenyl, cycloalkene base, alkynyl, aryl, aralkyl group, heterocycle and alkoxy and the substituted derivatives thereof. The nitrogen heterocyclic ring dual-carbene metal complex of the invention is prepared by the reaction between substituted imidazole salt and metallic compounds.
Description
Technical field
The invention belongs to organic synthesis and Organometallic Chemistry technical field, relate to the synthetic of N-heterocyclic carbine metal title complex, in particular ring-type nitrogen heterocyclic ring double carbine metal complex and preparation method thereof and application.
Background technology
Because the peculiar property of N-heterocyclic carbine has caused chemists' very big interest.Various stable the synthetic of N-heterocyclic carbine have promptly promoted the N-heterocyclic carbine CHEMICAL DEVELOPMENT with successfully separating.In nineteen sixty, Wanzlick etc. had carried out detailed research to thiazole-2-carbene (1) as reaction intermediate at that time to the research early start of N-heterocyclic carbine.Because unusual active of thiazole-2-carbene compounds, Wanzlick did not separate and obtained N-heterocyclic carbine at that time, but they recognize that the electronic effect of giving of N atom in ortho position in the imidazole ring can stablize Cabbeen center on the 2-position, and this lays a good foundation for later N-heterocyclic carbine CHEMICAL DEVELOPMENT.
The acquisition of research group's success of Arduengo in 1991 leader the free N-heterocyclic carbine, this achievement in research has promoted developing rapidly of N-heterocyclic carbine chemistry.They are at first reacted in tetrahydrofuran (THF) by two-(1-adamantyl) imidazole salts and sodium hydride, and a small amount of DMSO makes catalyzer, successfully separate having obtained stable N-heterocyclic carbine 2, and product is heat-staple crystal, and X-single crystal diffraction analytical method has been determined its structure.They used 1 again afterwards, and the 3-position is connected with the stable N-heterocyclic carbine that the less substituent imidazole salts of volume has made other types.Thereby make the N-heterocyclic carbine chemistry become one of research focus of organic chemistry filed in recent ten years.
The fluorescence molecule switch is the important component part of supramolecular chemistry.In order to reach the purpose of real simulation human brain thinking, be implemented in the interior control of organic molecule size range to electronics, scientists has proposed the imagination of development computer on molecular level.Through well-designed fluorescence molecule switch, can be developed into intelligentized biosensor.In addition, the fluorescence molecule switch is owing to can carry out switch motion according to the different stimulated of external environment, thereby it had obtained application in fields such as environmental analysis, clinical medicine and microtechniques in recent years.The fluorescence molecule switch that comprises metal ion match recent years has received scientist's very big concern, because metal ion match both can be as having the emitted fluorescence of delay group, also can be used as acceptor (mainly accepting the negatively charged ion object), also can serve a dual purpose simultaneously.The research of fluorescence molecule switch has become worldwide advanced subject.Fluorescence molecule switch great majority are structures of " fluorophore-matter-acceptor " type.Or the several so identical parts or the combination of distinct portions.Metal ion match has its unique distinction as the assembly of fluorescence molecule switch, promptly has characteristics such as highly sensitive, simple, reliable.By being widely used in fields such as life science, information science, environmental analysis, clinical medicine and microtechniques to its further investigation.
Summary of the invention
The present invention relates to ring-type nitrogen heterocyclic ring double carbine mercury, copper and silver complex and preparation method thereof.
The present invention also relates to preparation method as the dication heterocyclic precursor of this type of organometallic complex of preparation.
The present invention relates to this type of metal-organic hydrogen spectrum demarcates.
The crystalline that the present invention relates to this type of metallorganics is formed method, the research of take off data and data.
A metal-organic complex involved in the present invention is all cultivated by diffusion or evaporable method and is obtained.
A metal-organic complex involved in the present invention comprises the metal complexes described in the right 3,4,5.
A metal-organic complex involved in the present invention has all carried out the mensuration of nuclear magnetic data sign and fluorescence data.
The present invention further provides the method that under protection of inert gas, prepares nitrogen heterocyclic ring double carbine metal complex.And it is carried out crystallography characterize.
A metal-organic complex among the present invention is all measured and data characterization by x-ray diffractometer.
Technical scheme of the present invention is as follows:
Nitrogen heterocyclic ring double carbine metal complex with following chemical general formula:
M
nL(Y)
m
Wherein, M is the metallic cation of mercury, silver or copper;
N is 1 or 2;
L represents the two Cabbeens of the N-heterocycle that connects by durol;
Y represents halogen anion or hexafluoro-phosphate radical negative ion;
M represents the number of negative ion, and its value is 2.
Nitrogen heterocyclic ring double carbine of the present invention is selected from the compound of being represented by following formula:
Wherein, R
1, R
2Be independently or combine and be hydrogen, C
1-C
6Alkyl or C
1-C
6Organic radical, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, arylalkyl, nitrogen heterocyclic ring (as pyridine ring) or alkoxyl group.
Wherein, R
1And R
2, C
1-C
6Organic radical is selected from for example C of alkyl
2H
5, C
6H
13, branched-chain alkyl isobutyl-, neo-pentyl, alkynyl ethynyl, alkoxyl group for example benzyl, menaphthyl, nitrogen heterocyclic ring and substitutive derivative thereof for example (ethyl imidazol(e), normal-butyl imidazoles, ethyl benzo imidazole, normal-butyl benzo imidazoles, 1-picolyl benzoglyoxaline) of oxyethyl group, aryl for example for example for example.
The preferred nitrogen heterocyclic ring double carbine metal complex of the present invention is selected from the compound of following formula:
Wherein R is selected from hydrogen, C
1-C
6Alkyl, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, nitrogen heterocyclic ring (as pyridine ring) or alkoxyl group.C
1-C
6Organic radical is selected from for example C of alkyl
2H
5, C
6H
13, branched-chain alkyl isobutyl-, neo-pentyl, alkynyl ethynyl, alkoxyl group for example benzyl, menaphthyl, nitrogen heterocyclic ring and substitutive derivative thereof for example (ethyl imidazol(e), normal-butyl imidazoles, ethyl benzo imidazole, normal-butyl benzo imidazoles, 1-picolyl benzoglyoxaline) of oxyethyl group, aryl for example for example for example.
The hydrargyrum complex of another preferred shielded ring-type N-heterocyclic carbine of the present invention is the compound that is expressed from the next:
The copper complex of another preferred shielded ring-type N-heterocyclic carbine of the present invention is the compound that is expressed from the next:
Disclosed nitrogen heterocyclic ring double carbine metal complex is a relation arranged side by side among the present invention, does not have the branch of preferential primary and secondary.
The preparation method of nitrogen heterocyclic ring double carbine metal complex of the present invention; it is characterized in that: under the protection of rare gas element (as nitrogen); the ratio that nitrogen heterocyclic ring double carbine salt that will connect by tetramethyl-benzene and metallic compound with the mol ratio are 0.5-3～2-5 joins in the reaction vessels; after the high-purity organic solvent dissolving that dewaters; under 0 ℃～100 ℃ temperature, reacted 12～24 hours; filter, volatilization obtains the carbine metal title complex.
Metallic compound of the present invention is selected from wherein a kind of in potassium tert.-butoxide, sodium tert-butoxide, sodium hydride, hydrolith, silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide, cuprous halide, cuprous iodide, Red copper oxide, Quilonum Retard, nickel acetate, Cu Suan Palladium, zirconium white, yttrium oxide, the lanthanum trioxide.Preferred Silver monoacetate, silver carbonate, mercury halide, Red copper oxide, nickel acetate, Cu Suan Palladium or zirconium white.Be more preferably silver suboxide, Glacial acetic acid mercury or cuprous iodide.
Organic solvent of the present invention is selected from tetrahydrofuran (THF) (THF), methylene dichloride, 1,2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, N, any one or its mixture in dinethylformamide, the dimethyl sulfoxide (DMSO).Preferred acetone, 1,2-ethylene dichloride, N, dinethylformamide or dimethyl sulfoxide (DMSO) are more preferably tetrahydrofuran (THF) (THF), methylene dichloride or acetonitrile.Wherein mixed solvent is the mixing solutions of THF and methylene dichloride.
The present invention further discloses the feasibility of nitrogen heterocyclic ring double carbine metal complex as the raw material of preparation fluorescent material.Experimental results show that: the fluorescent emission intensity of nitrogen heterocyclic ring double carbine metal complex is than corresponding part stronger (strong 2-3 doubly), and change in fluorescence is obvious.At 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 232nm condition in the solution, and the fluorogram of title complex and respective ligand thereof is seen Figure 10, Figure 11.
The nitrogen heterocyclic ring double carbine metal complex that the present invention proposes is a kind of senior fluorescent material that can stable existence under standard state, have Adjustable structure and put in order, prepare succinct, the tangible advantage of fluorescence photosensitive effect, can be used for making fluorescent material and fluorescence molecule switch identification system, be expected to be applied in the fluorescence chemical field.
Description of drawings:
Fig. 1 is 1,4-two [1-ethyl-3-imidazoles methyl]-2,3,5,6-tetramethyl-benzene bromide crystalline structure figure;
Fig. 2 is for containing the yellow crystals structure iron of silver complex (preparation example 10);
Fig. 3 is for containing the pale yellow crystals structure iron of hydrargyrum complex (preparation example 11);
Fig. 4 is for containing the pale yellow crystals structure iron of copper complex (preparation example 12);
Fig. 5 is at 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 232nm condition in the solution, the fluorogram of title complex and respective ligand thereof (application example 13).Wherein-the expression title complex ... the fluorescence emission spectrogram of expression part.
Fig. 6 is at 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 232nm condition in the solution, the fluorogram of title complex and respective ligand thereof (application example 14).Wherein-the expression title complex ... the fluorescence emission spectrogram of expression part.
Table 1 is part (preparation example 1) and the crystal parameters that contains hydrargyrum complex (preparation example 11)
Table 1
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, what be illustrated especially is, the initial substance 1 of preparation The compounds of this invention, 4-dioxane, 2,3,5,6-tetramethyl--1,4-xylylene bromide, ethyl imidazol(e), normal-butyl benzo imidazoles, ammonium hexafluorophosphate etc. all can have been bought or easily made by known method from the market.
2,3,5,6-tetramethyl--1, the 4-xylylene bromide is by literature method preparation (A.W.van der Made, R.H.van der Made, J.Org.Chem.1993,58,1262).Normal-butyl benzo imidazoles is by literature method preparation (Q.X.Liu, F.B.Xu, Q.S.Li, H.B.Song, Z.Z.Zhang, Organometallics 2004,23,610).The used reagent of preparation The compounds of this invention all derives from upright chemical industry company limited of Tianjin unit, and rank is an analytical pure.
What need in addition to be illustrated is: all experimental implementation utilization Schlenk technology, solvent is through the normal process purifying.To be useful on reagent synthetic and that analyze all be analytical pure, not through further handling.Fusing point is measured by the Boetius block apparatus.
1H and
13C{
1The H}NRM spectrum is by mercury variable V x300 spectrophotometer record, between measurement zone: 300MHz and 75MHz.Chemical shift, δ is with reference to the TMS mensuration of international standard.
Preparation example 1
1, add 2,3,5 in the 4-dioxane (50mL), 6-tetramethyl--1, the 4-xylylene bromide (3.000g, 9.370mmol) and ethyl imidazol(e) (1.980g 0.021mol), stirred 3 days down at 90 ℃, a large amount of gray precipitate of appearance in the solution.Filter,, obtain 1,4-two [1-ethyl-3-imidazoles methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene bromide with the ether washing.Productive rate: 4.580g (95.4%).Mp：254-260℃。
1H?NMR(300MHZ，CDCl
3)：δ1.49(t，J＝7.3，6H，CH
3)，2.17(s，12H，CH
3)，4.44(q，J＝7.3，4H，CH
2)，5.75(s，4H，CH
2)，7.31(s，2H，imiH)，8.50(s，2H，imiH)，9.87(s，2H，imiH)(imi：imidazole)。
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 1, and crystal parameters is seen specification sheets subordinate list 1.
Preparation example 2
1, add 2,3,5 in the 4-dioxane (50mL), 6-tetramethyl--1, (3.000g, 9.370mol) (2.560g 0.021mol), stirred 3 days down at 90 ℃ the 4-xylylene bromide, occurred a large amount of gray precipitate in the solution with the normal-butyl imidazoles.Filter,, obtain 1,4-two [1-normal-butyl-3-imidazoles methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene bromide with the ether washing.Productive rate: 4.500g (84.4%).Mp：282-286℃。
1H?NMR(300MHZ，CDCl
3)：δ0.90(t，J＝5.3，6H，CH
3)，1.35(m，4H，CH
2)，1.85(t，J＝5.3，4H，CH
2)，2.13(s，12H，CH
3)，4.40(t，J＝5.3，4H，CH
2)，5.80(s，4H，CH
2)，7.33(s，2H，imiH)，8.54(s，2H，imiH)，9.90(s，2H，imiH)(imi：imidazole)。
Its experiment flow is as shown below:
Preparation example 3
1, add 2,3,5 in the 4-dioxane (50mL), 6-tetramethyl--1, the 4-xylylene bromide (2.000g, 6.250mol) and ethyl benzo imidazole (2.013g 0.014mol), stirred 3 days down at 90 ℃, a large amount of gray precipitate of appearance in the solution.Filter,, obtain 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene bromide with the ether washing.Productive rate: 3.300g (86.2%).Mp：170-174℃。
1H?NMR(300MHZ，CDCl
3)：δ1.62(t，J＝7.3，6H，CH
3)，2.31(s，12H，CH
3)，4.84(q，J＝7.3，4H，CH
2)，5.90(s，4H，CH
2)，7.78(m，6H，PhH)，7.31(s，2H，imiH)，8.52(d，J＝8.3，2H，PhH)，10.40(s，2H，imiH)(imi：imidazole)。
Its experiment flow is as shown below:
Preparation example 4
1, add 2,3,5 in the 4-dioxane (50mL), 6-tetramethyl--1, (2.000g, 6.3mmol) (2.398g 14mmol), stirred 3 days down at 90 ℃ the 4-xylylene bromide, occurred a large amount of gray precipitate in the solution with normal-butyl benzo imidazoles.Filter,, obtain 1,4-two [normal-butyl-3-benzoglyoxaline methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene bromide with the ether washing.Productive rate: 3.060g (72.9%).Mp：266-268℃。
1HNMR(300MHZ，CDCl
3)：δ0.93(t，J＝7.3，6H，CH
3)，1.41(m，2H，CH
2)，1.96(m，2H，CH
2)，2.30(s，12H，CH
3)，4.79(t，J＝7.3，4H，CH
2)，5.93(s，4H，CH
2)，7.81(m，6H，PhH)，8.60(d，J＝8.3，2H，PhH)，10.47(s，2H，imiH)(imi：imidazole).
Its experiment flow is as shown below:
Preparation example 5
1, add 2,3,5 in the 4-dioxane (50mL), 6-tetramethyl--1, (1.000g, 3.125mmol) (1.300g 6.25mmol), stirred 3 days down at 90 ℃ the 4-xylylene bromide, occurred a large amount of gray precipitate in the solution with 1-picolyl benzoglyoxaline.Filter,, obtain 1,4-two [1 '-picolyl-3-benzoglyoxaline methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene bromide with the ether washing.Productive rate: 3.200g (72.8%).Mp：324-326℃。
1H?NMR(300MHZ，CDCl
3)：δ2.31(s，12H，CH
3)，5.90(s，4H，CH
2)，5.94(s，4H，CH
2)，7.36(m，2H，PhH)，7.66(m，6H，PhH)，7.95(m，4H，PhH)，8.14(m，2H，PhH)，8.42(d，J＝4.8，2H，PhH)，9.98(s，2H，imiH)(imi：imidazole).
Its experiment flow is as shown below:
Preparation example 6
With 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide (2.000g, (100mL) solution of methyl alcohol 3.3mmol) and ammonium hexafluorophosphate (1.171g, 7.2mmol) methyl alcohol (100mL) solution mix, at room temperature stir 24h, separate out the grey powder.Filter, solid is washed with methyl alcohol, obtains 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5, the grey powder of 6-tetramethyl-benzene hexafluorophosphate.Productive rate: 1.980g (81.8%).Mp：292-296℃。
1H?NMR(300MHZ，CDCl
3)：δ1.66(t，J＝7.2，6H，CH
3)，2.44(s，12H，CH
3)，4.89(q，J＝7.3，4H，CH
2)，5.95(s，4H，CH
2)，7.67(m，6H，PhH)，7.81(s，2H，imiH)，8.55(d，J＝8.3，2H，PhH)，10.60(s，2H，imiH)(imi：imidazole)。
Its experiment flow is as shown below:
Preparation example 7
In methylene dichloride (30mL), add 1,4-two [1-normal-butyl-3-imidazoles methyl]-2,3,5, and 6-tetramethyl-benzene bromide (0.200g, 0.4mmol), silver suboxide (0.089g, 0.4mmol) and sodiumazide (0.050g, 0.8mmol), this aaerosol solution refluxed 1 day at 40 ℃, filter, filtrate is concentrated to 15mL, standing over night, obtain the white crystal of title complex, this title complex is stable under the condition of air and humidity.Productive rate: 0.078g (31.3%), Mp:160-162 ℃.
1H?NMR(300MHZ，CDCl
3)：δ0.93(t，J＝5.3，6H，CH
3)，1.41(m，4H，CH
2)，1.87(t，J＝5.3，4H，CH
2)，2.16(s，12H，CH
3)，4.45(t，J＝5.3，4H，CH
2)，5.84(s，4H，CH
2)，7.38(s，2H，imiH)，8.60(s，2H，imiH)，9.93(s，2H，imiH)(imi：imidazole)。
Its experiment flow is as shown below:
Preparation example 8
In methylene dichloride (30mL), add 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene hexafluorophosphate (0.200g, 0.3mmol) and silver suboxide (0.062g, 0.3mmol), this aaerosol solution refluxed 1 day at 40 ℃, filter, filtrate is concentrated to 15mL, and standing over night obtains the white powder of title complex.Productive rate: 0.065g (34.4%), Mp:256-260 ℃.
1H?NMR(300MHZ，DMSO-d
6)：δ1.50(t，J＝5.1，6H，CH
3)，2.43(s，12H，CH
3)，4.46(q，J＝5.1，4H，CH
2)，5.53(s，4H，CH
2)，7.51(m，4H，PhH)，7.84(d，J＝5.4，2H，PhH)，8.33(d，J＝5.4，2H，PhH).
Its experiment flow is as shown below:
Preparation example 9
In methylene dichloride (30mL), add 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide (0.200g, 0.327mmol) and silver suboxide (0.075g, 0.359mmol) this aaerosol solution refluxed 1 day at 40 ℃, filtered, filtrate is concentrated to 15mL, standing over night obtains the yellow crystals of title complex, and this title complex is stable under air and moist condition.Productive rate: 0.087g (32.2%), fusing point: 194-196 ℃.Anal.Calcdfor?C
30H
34N
4Br
2Ag
2：C，43.61；H，4.15；N，6.78％.Found：C，43.52；H，4.47；N，6.54％.
1H?NMR(300MHZ，CDCl
3)：δ1.68(t，J＝7.3，6H，CH
3)，2.35(s，12H，CH
3)，4.88(q，J＝7.3，4H，CH
2)，5.86(s，4H，CH
2)，7.33(m，6H，PhH)，8.56(d，J＝8.3，2H，PhH).
13C?NMR(75MHZ，DMSO-d
6)：δ170.0(C
carbene)，137.9，133.7，129.2，118.8and?113.9(PhC)，53.1(NCH
2Ph)，48.0(NCH
2C)，13.5(CCH
3)，9.0(PhCH
3).
Its experiment flow is as shown below:
Preparation example 10
In methylene dichloride (30mL), add 1,4-two [1 '-picolyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide (0.200g, 0.271mmol) and silver suboxide (0.070g, 0.298mmol) this aaerosol solution refluxed 1 day at 40 ℃, filtered, filtrate is concentrated to 15mL, standing over night obtains the yellow crystals of title complex, and this title complex is stable under air and moist condition.Productive rate: 0.081g (31.2%), fusing point: 288-290 ℃.
1H?NMR(300MHZ，CDCl
3)：δ2.30(s，12H，CH
3)，5.91(s，4H，CH
2)，5.95(s，4H，CH
2)，7.34(m，2H，PhH)，7.61(m，6H，PhH)，7.92(m，4H，PhH)，8.13(m，2H，PhH)，8.44(d，J＝4.8，2H，PhH).
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 2.
Preparation example 11
In acetonitrile (30mL), add with 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide (0.200g, 0.326mmol) and Glacial acetic acid mercury (0.114g, 0.359mmol) this aaerosol solution refluxed 1 day at 40 ℃, filtered, filtrate is concentrated to 15mL, standing over night obtains the buff powder of title complex.Productive rate: 0.128g (39.7%).Mp：306-308℃.
1H?NMR(300MHZ，DMSO-d
6)：δ1.59(t，J＝7.2，6H，CH
3)，2.27(s，12H，CH
3)，4.62(q，J＝7.2，4H，CH
2)，5.82(s，4H，CH
2)，7.72(s，4H，PhH)，8.02(d，J＝6.2，2H，PhH)，8.28(d，J＝6.2，2H，PhH)。
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 3, and crystal parameters is seen specification sheets subordinate list 1.
Preparation example 12
In methylene dichloride (30mL), add 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene hexafluorophosphate (0.2000g, 0.269mmol) and cuprous iodide (0.100g, 0.538mmol) this aaerosol solution refluxed 1 day at 40 ℃, filtered, filtrate is concentrated to 15mL, standing over night obtains the white powder of title complex.Productive rate: 0.126g (56.3%), Mp:352-354 ℃.
1H?NMR(300MHZ，DMSO-d
6)：δ1.41(t，J＝5.1，6H，CH
3)，2.36(s，12H，CH
3)，4.40(q，J＝5.1，4H，CH
2)，5.49(s，4H，CH
2)，7.49(m，4H，PhH)，7.80(d，J＝5.4，2H，PhH)，8.3(d，J＝5.4，2H，PhH).
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 4.
Application example 13
With embodiment 9 prepared complex crystals, be made into certain density dichloromethane solution (1 * 10
-5Mol/L).By liquid testing fluorescence: the part of the fluorescence emission spectrum strength ratio correspondence of title complex is stronger, and change in fluorescence is obvious.At 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 232nm condition in the solution, wherein-and the expression title complex ... the fluorescence emission spectrogram of expression part.The fluorogram Figure of description 5 of title complex and respective ligand thereof.
Application example 14
With embodiment 11 prepared complex crystals, be made into certain density dichloromethane solution (1 * 10
-5Mol/L).By liquid testing fluorescence: the part of the fluorescence emission spectrum strength ratio correspondence of title complex is stronger, and change in fluorescence is obvious.At 298K, CH
2Cl
2(1 * 10
-5Mol/L) excitation wavelength is under the 232nm condition in the solution, the fluorogram of title complex and respective ligand thereof (application example 14).Wherein-and the expression title complex, the fluorescence emission spectrogram of expression part.The fluorogram Figure of description 6 of title complex and respective ligand thereof.
X-ray crystal structure is measured
Crystal data and structure refinement parameter are included in the supportive information.Carry out on Bruker SMART 1000CCD diffractometer, experimental temperature is 293 (2) K, under 50kV and 20mA, with Mo-K α radiation
Operation is carried out data gathering and reduction with SMART and SAINT software, and the scope of θ is 1.8＜θ＜25 °.Use the SADABS program and carry out experience absorption rectification.Crystalline structure is solved by direct method, with the SHELXTL bag whole non-hydrogen atom coordinate anisotropy thermal parameters is carried out the complete matrix least-squares refinement.
In sum, among the embodiment that content of the present invention is not confined to, the knowledgeable people in the same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment comprises within the scope of the present invention.
Claims (5)
1. the nitrogen heterocyclic ring double carbine metal complex that has following chemical general formula:
2. method for preparing the described nitrogen heterocyclic ring double carbine metal complex of claim 1, it is characterized in that: in the 30mL acetonitrile, add 0.200g 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide and 0.114g Glacial acetic acid mercury, this aaerosol solution refluxed 1 day at 40 ℃, filtered, and filtrate is concentrated to 15mL, standing over night obtains the buff powder of title complex.
3. the nitrogen heterocyclic ring double carbine metal complex that has following chemical general formula:
4. method for preparing the described nitrogen heterocyclic ring double carbine metal complex of claim 3, it is characterized in that: in the 30mL methylene dichloride, add 0.200g 1,4-two [ethyl-3-benzoglyoxaline methyl]-2,3,5,6-tetramethyl-benzene bromide and 0.075g silver suboxide, this aaerosol solution refluxed 1 day at 40 ℃, filtered, and filtrate is concentrated to 15mL, standing over night obtains the yellow crystals of title complex.
5. claim 1 or the 3 described nitrogen heterocyclic ring double carbine metal complexes application in the preparation fluorescent material.
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| CN102225942A (en) * | 2011-04-28 | 2011-10-26 | 华南理工大学 | Preparation method of N-heterocyclic carbine copper complex |
| CN102286006B (en) * | 2011-06-29 | 2013-07-17 | 天津师范大学 | Ether-chain bridged bis-benzimidazole metal complexes and preparation method and application thereof |
| CN102584864B (en) * | 2012-01-12 | 2014-09-17 | 天津师范大学 | Azacyclo-carbene metal crown ether and application of azacyclo-carbene metal crown ether to identification of objects |
| CN102807591B (en) * | 2012-07-30 | 2014-09-17 | 天津师范大学 | Double benzimidazole ligand based metal complex and preparation method and application thereof |
| CN103254217B (en) * | 2013-04-12 | 2015-05-13 | 天津师范大学 | Metal complexes with durene-bridged bibenzimidazole as ligand, and preparation method and application thereof |
| CN103232478B (en) * | 2013-04-12 | 2016-04-20 | 天津师范大学 | Based on metal complexes and preparation method thereof and the purposes of bidentate benzoglyoxaline part |
| CN103242300B (en) * | 2013-04-15 | 2014-06-25 | 天津师范大学 | N-heterocyclic carbene metal complex based on quinoxaline as well as preparation method and application thereof |
| CN103497208B (en) * | 2013-09-30 | 2016-04-20 | 天津师范大学 | Based on Benzimidazole bidentate ligand metal complexes and preparation method thereof and purposes |
| CN104650120B (en) * | 2013-11-19 | 2017-06-13 | 中国科学院上海有机化学研究所 | Difluoromethyl silver compound, monocrystalline, synthetic method and application |
| CN103665009A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,4-di-(1-H-benzimidazolyl) butane-silver(I) complex and preparation method thereof |
| CN104230965B (en) * | 2014-09-04 | 2016-04-06 | 天津师范大学 | The preparation of ring-type silver complex and the application in identification object thereof |
| CN104910138A (en) * | 2015-05-13 | 2015-09-16 | 天津师范大学 | Bis-benzimidazole salts based on sym-trimethylbenzene bridging, preparation method therefor and applications |
| CN105175344B (en) * | 2015-08-10 | 2018-05-29 | 广西医科大学 | A kind of silver-colored (I) complex of 1,3- bisbenzimidazoles benzene and its application in pharmacy |
| CN111100147B (en) * | 2018-10-25 | 2022-11-04 | 中国石油化工股份有限公司 | Synthesis method of copper-nitrogen heterocyclic carbene complex catalyst |
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